Hydrogen bonding from a valence bond theory perspective: the role of covalency.

A valence bond theory based method has been developed to decompose hydrogen bond energies into contributions from geometry, electrostatics, polarization and charge transfer. This decomposition method has been carried out for F-HFH, F-HOH2, F-HNH3, HO-HOH2, HO-HNH3, and H2N-HNH3. Localized valence bond self-consistent field (L-VBSCF) and localized breathing orbital valence bond (L-BOVB) calculations were performed at the PBEPBE/aug-cc-pVDZ optimized geometries. It is shown that inclusion of valence bond structures that explicitly include charge transfer account for at least 32% (likely over half) of the hydrogen bond energy of all systems studied, indicating the dominant role of covalency. This is in agreement with calculated bond lengths, geometry deformation energies, and polarization energies. Electrostatic effects were found to play only a minor role in contrast to some widely held ideas regarding the nature of hydrogen bonding.

Ultrafast proton-assisted tunneling through ZrO2 in dye-sensitized SnO2-core/ZrO2-shell films.

Core-shell architectures are used to modulate injection and recombination in dye-sensitized photoelectrochemical cells. Here, we demonstrate that exposing SnO2-core/ZrO2-shell films to acid permits photoinduced electron transfer through ZrO2-shells at least 4 nm thick. A novel mechanism of charge transfer is proposed where protonic defects permit ultrafast trap-assisted tunneling of electrons.

A Terahertz-Transparent Electrochemical Cell for In Situ Terahertz Spectroelectrochemistry.

Terahertz spectroscopy is broadly applicable for the study of a wide variety of materials, but spectroelectrochemistry has not been performed in the THz range because of the lack of a THz-transparent electrochemical cell. While THz-transparent electrodes do exist, they have never been utilized in a complete three-electrode cell, which is the configuration required for accurate potential control in aqueous media. We have designed and constructed a THz-transparent three-electrode electrochemical cell and have performed THz spectroelectrochemistry of a SnO2 thin film. The cell utilizes a custom-made reference electrode and tubing which allows the composition of electrolyte to be changed during an experiment. THz spectroelectrochemical measurements show a decrease in THz transmission at potentials where SnO2 conduction band states are potentiostatically filled. We also describe a simple method for measuring the uncompensated resistance and RC time constant.

Highly Active NiO Photocathodes for H2O2 Production Enabled via Outer-Sphere Electron Transfer.

Tandem dye-sensitized photoelectrosynthesis cells are promising architectures for the production of solar fuels and commodity chemicals. A key bottleneck in the development of these architectures is the low efficiency of the photocathodes, leading to small current densities. Herein, we report a new design principle for highly active photocathodes that relies on the outer-sphere reduction of a substrate from the dye, generating an unstable radical that proceeds to the desired product. We show that the direct reduction of dioxygen from dye-sensitized nickel oxide (NiO) leads to the production of H2O2. In the presence of oxygen and visible light, NiO photocathodes sensitized with commercially available porphyrin, coumarin, and ruthenium dyes exhibit large photocurrents (up to 400 µA/cm2) near the thermodynamic potential for O2/H2O2 in near-neutral water. Bulk photoelectrolysis of porphyrin-sensitized NiO over 24 h results in millimolar concentrations of H2O2 with essentially 100% faradaic efficiency. To our knowledge, these are among the most active NiO photocathodes reported for multiproton/multielectron transformations. The photoelectrosynthesis proceeds by initial formation of superoxide, which disproportionates to H2O2. This disproportionation-driven charge separation circumvents the inherent challenges in separating electron-hole pairs for photocathodes tethered to inner sphere electrocatalysts and enables new applications for photoelectrosynthesis cells.

Exploring the solid state phase transition in dl-norvaline with terahertz spectroscopy.

dl-Norvaline is a molecular crystal at room temperature and it undergoes a phase transition when cooled below 190 K. This phase transition is believed to be Martensitic, thus making it of particular interest for molecular machines. In this paper we investigate this phase transition by measuring its terahertz (THz) spectrum over a range of temperatures. Temperature-dependent THz time-domain spectroscopy (THz-TDS) measurements reveal that the transition temperature (Tß→α) is 190 K. The influence of nucleation seeds was analyzed by determining the Tß→α of molecular crystals with varying grain size. Grains of 5 µm or less result in a lower transition temperature (Tß→α = 180 K) compared to larger grains of 125-250 µm (Tß→α = 190 K). Additionally, we gain insight into the physical process of the phase transition via temperature-dependent THz-TDS spectra of doped and mixed molecular crystals. The addition of molecular dopants, which differ from dl-norvaline only at the end of the side chain which resides in the hydrophobic layers of the crystal, decreases Tß→α. This is consistent with a solid-solid phase transition in which the unit cell shifts along this hydrophobic layer, and it leads us to believe that the phase transition in dl-norvaline is Martensitic in nature.

Dynamics of Electron Injection in SnO2/TiO2 Core/Shell Electrodes for Water-Splitting Dye-Sensitized Photoelectrochemical Cells.

Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) rely on photoinduced charge separation at a dye/semiconductor interface to supply electrons and holes for water splitting. To improve the efficiency of charge separation and reduce charge recombination in these devices, it is possible to use core/shell structures in which photoinduced electron transfer occurs stepwise through a series of progressively more positive acceptor states. Here, we use steady-state emission studies and time-resolved terahertz spectroscopy to follow the dynamics of electron injection from a photoexcited ruthenium polypyridyl dye as a function of the TiO2 shell thickness on SnO2 nanoparticles. Electron injection proceeds directly into the SnO2 core when the thickness of the TiO2 shell is less than 5 Å. For thicker shells, electrons are injected into the TiO2 shell and trapped, and are then released into the SnO2 core on a time scale of hundreds of picoseconds. As the TiO2 shell increases in thickness, the probability of electron trapping in nonmobile states within the shell increases. Conduction band electrons in the TiO2 shell and the SnO2 core can be differentiated on the basis of their mobility. These observations help explain the observation of an optimum shell thickness for core/shell water-splitting electrodes.

Proton-Induced Trap States, Injection and Recombination Dynamics in Water-Splitting Dye-Sensitized Photoelectrochemical Cells.

Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) utilize a sensitized metal oxide and a water oxidation catalyst in order to generate hydrogen and oxygen from water. Although the Faradaic efficiency of water splitting is close to unity, the recombination of photogenerated electrons with oxidized dye molecules causes the quantum efficiency of these devices to be low. It is therefore important to understand recombination mechanisms in order to develop strategies to minimize them. In this paper, we discuss the role of proton intercalation in the formation of recombination centers. Proton intercalation forms nonmobile surface trap states that persist on time scales that are orders of magnitude longer than the electron lifetime in TiO2. As a result of electron trapping, recombination with surface-bound oxidized dye molecules occurs. We report a method for effectively removing the surface trap states by mildly heating the electrodes under vacuum, which appears to primarily improve the injection kinetics without affecting bulk trapping dynamics, further stressing the importance of proton control in WS-DSPECs.